Dissociated starch and method of making the same



March 25, 1941. G. v. CAESAR Erm. 2,417,969y

DISSOCIATED STARCHAND METHOD OF HRKING THE SME I Filed Dec. 15, 1941 2 Sheets-Sheet 1 FIGA. BY

Much 25,1941. Y G. v. CAESAR mL 2,417,969

DlSSOCIATED STARCH AND IETHOD 0F MAKING THE SAIE r V l Patented Mar. 25, i947 time DISSO\ CIATED STARCH AND METHOD F MAKING THE SAME George V. Caesar,

Thomas D. Thompson,

signors to Stein Staten Island, N. Y., and

North Branch, N. J., as- Hall & Company, Inc., New

York, N. Y., a corporation of New York Application December 15, i941, Serial No. 423,046

9 Claims.' (Cl. 127-32) The present invention relates to a new starch product having unique characteristics with respect to its physical and chemical properties. The invention also resides in a method of-mechanically treating starch to produce the new starch composition'havin-g improved properties, for example, with respect to viscous characteristics, structure, and film-forming properties. The industrial` use of aqueous dispersions of starch, familiarly but less correctly known as starch solutions, is largely predicated upon a suitable degree of colloidal homogeneity and viscous flow at the solid concentrations desired. Starch dispersions are used for very many industrial purposes, chief among which are paperV and textile sizing and coating, and adhesive usages. A tough homogeneous film is desired, and the aqueous dispersion from which such a iilm is deposited should preferably exhibit the maximum possible degree of viscous stability as a function of temperature and time.

more or less by mechanical agitation from stir-- ring mechanisms, pumps, colloid mills, etc. For starches which may have been considerably degenerated by such pretreatments, comparatively little mechanical agitation may be employed. The extent ton which mechanical means of dispersion may be used, depends upon individual mill equipment and practice.

Modication of the starch to make the same soluble in cold water has been unsuccessful in that some of the desirable properties of a conventional starch solution are destroyed. The art long has sought to prepare a starch product which is soluble in cold water and which at the same time has optimum characteristics with respect to viscosity and nlm-forming' properties.

In accordance with the present invention, a new starch product may be prepared which is soluble inV cold water, and solutions prepared o therefrom exhibit improved characteristics, in-

Raw starch in its usual commercial form is insoluble in water but may be formed into a colloidal or semi-colloidal dispersion by forming a slurry with water and heating the starch slurry to an elevated temperature at which the starch granules swell or burst and thus become gelatinized. The particular temperature required for gelatinization depends upon the particular starch selected and on other conditions maintained during the gelatinization. The properties of such gelatinized dispersions depend upon many factors such as temperature and concentration, and also upon the starch -material itself and the manner in/which the dispersion is prepared. It is to be expected that many attempts have been made heretofore to modify the properties of starch to enhance the usefulness of the material for the many above mentioned purposes.

Unfortunately, these desiderata of homogeneity, suitable viscosity range, and viscous stability have heretofore been difficult if not impossible to approximate using low cost raw, substantially unmodified starches. modify raw starch through suitable chemical 0r enzymic treatments.

-Among the expedients utilized to modify the characteristics of starch heretofore is the treatment of starch with various chemical reagents such as acids, alkalis and oxidizing compounds.

Such pretreatments bring about to a greater 'or less extent a degeneration or depolymerization of 1 the starch structure, forming a fine-grained liquid structure when the processed starch is dispersed in water through cooking, accompanied It is postulated that It has been necessary to Y cluding, for example, an exceptionally low and stable viscosity as a function of temperature. Moreover, the product is of novel appearance and otherwise is particularly suitable for use in conventional textile and paper treating processes, as described more fully hereinafter.

The invention may be understood in connection with the drawings, in which:

Fig. 1 is a diagrammatic illustration of a specific example of the process of practicing the invention;

Fig. 2 is a diagrammatic illustration of certain properties of the composition produced in accordance with the invention` as compared ywith prior art compositions.

We have referred previously tok degeneration or depolymerzation of starch structures, and before proceeding with a more detailed description of the invention, it is desirable to consider some of the considerations in starch chemistry. the starch molecules occur in relatively large aggregates that may be broken up into smaller ones. Such smaller aggregates 'differ in many respects depending on their structure and the manner in which they are formed. It has been assumed that the starch molecule is a curved chain of uncertain and perhaps varimum area of orifice.

termed degeneration or depolymerization; it is involved, forexample, when starch is converted into dextrin. The breaking ofthe secondary valences to separate the chains is assumed to be another phenomenon and is termed dissociation or dls organization.

- It is believed that the starch aggregates in dissociation of the starch granular package, with minimum depolymerization or degeneration of the molecule, may-be obtained when an aqueous suspension of the granules is sheared one against another by turbulent impact, during hydration or swelling.

The process of this invention comprising the physical treatment of starch while it is undergoing the abovetreatment may be accomplished by continuously circulating a starch milk of suspended granules under high pressure induced by a suitable pumping mechanism and to obtain maximum turbulence by the use of a square or knife-edged orifice of variable dimensions, applying only enough external heating to carry the starch milk slowly through its gelatinization phase. In practice it was found that no external heating was required, the heat generated by the turbulent impacts of the granules being suilicient automatically to raise the temperature of the charg to any degree desired.

It was found to be unnecessary andin certain respects undesirable to carry the process very far beyond the peak pressure developed at the opti- The hydrostatic gauge pressuresincrease with time until a peak pressure at maximum gelatinization is obtained; after that the pressure falls rather slowly. Further processing is uneconomical, the energy being expended against elastic particles as in the case of ordinary homogenizing processes, Long continued heating and processing was found to yield delinite evidences of degeneration.

The invention is to be distinguished from the mechanical treatment, such as homogenizing, subsequent to gelatinization, which is not ellective for obtaining the results of this invention.

In certain instances,` raw starch aqueous dispersions have been drastically processed by homogenizing through pumps, injectors, colloid mills, etc., for prolonged periods at elevated temperatures; but substantially au of this meehnt, cal energy has been expended upon the veryA elastic medium of substantially gelatiniz'ed starch granules and fragmentsl of granules. It is ex ceedingly diiiicult and wasteful of energy to do useful work upon such an elastic medium, as the relatively ineicient results have'proven. Dissociation df aqueous starch dispersions by-these methods has not been commercially successful except for minor usages wherein processing costs were relatively unimportant. Nor have the products l' so obtained possessed to an equal degree the physical properties of nlm-forming toughness, viscous stability, and the freedom from excessive depolymerization yor degeneration characteristic properties' more resembling those 30 should, have sharp or square edges.

of the products of the processfor which we claim invention. u t

Qur process is also'in'contrast to a process of Ardry grinding or'shearing ofthe starch granules, whichl develops a high degree of localized heat and 'degenerative influences.

In accordance with'the present invention, a suspension or milk of raw starch is prepared at a concentration of the onder ofabout 5 to 30% l0 solids, preferably within the range of 10 to 20%.

The milk, initially, is preheated, while under agiu tation to prevent settling, to a temperature preferably well below the gelatinizingtemperature for the particular starch selected. It is advantageous to discontinue the preheating at a temperature of about' 10 below the temperature at 'Y which gelatinization begins. For tapioca flour and potato starch, the slurry will be heated to about 120 to 130 F. The preheating may be carried out in any suitable fashion, i'or example,

in the container in which the starch slurry is to be processed subsequently or in a separate container. 'The processing container or kettle preferably vcontains a suitable agitator and is equipped to circulate the starch gmilk or' slurry continuously by means of a suitably designed high pressure pump discharging through a suitable type of orice back into the kettle. 'Ihe orifice preferably This provides maximum turbulency as the slurry passes through and exitsfrom the orice; By this -means the liquid mass in the processing kettle may be continuously circulatedunder high pressure through an orifice throughout the processing operation. The cross-section of the orifice is adjusted during the beginning of an operation to yield a gauge pressure such that the heat generated by the collision impacts of the starch 40 granules is suiilcient automatically to supply the heat required Afor gelatinization. This should be at least a pressure of the order of 200 pounds per square inch, and preferably not less than about 300 pounds per square inch. It will be obvious that the pressure may be varied over a wide range, depending upon the particular starch selected and upon the limits of the processing apparatus utilized.

The opening of the orifice thereafterlis permitted to remain in the initial position butthe gauge pressure will. increase as the result of an increase in the viscosity of the starch solution as it undergoes gelatinization. The heat generated by the rapid pumping of the starch solution at high pressures slowly increases the temperature of the mass. When a temperature has been attained approximating the gelatinization temperature of the starch, the granules begin progressively and rapidly to swell or hydrate, in

accordance with well-recognized facts of starch behavior. It is Well known/that gelatinization does not take place instantly at a fixed temperature but proceeds gradually through a temperature range. Apparently some of the starch micelles gelatinize at a slightly lower temperature than others. The rate of temperature rise also increases, and as is well known, this depends on the rate at which work is done on the starch slurry, and also to some extent on the concentration of solids and pressure. and the insulation in the kettle and pump line. Such .increase in temperature correspondingly increases the rate ofgelatinization. The gelatinization zone Cmay be technically described as a semi-rigid phase, the suspended starch gran# ,tend

ules being more yor less partly swollen or semirigid. In this physical condition they have attained their maximum degree of susceptibility to destruction or disorganiz'ation through shearing forces induced by the high velocity of turbulent ilow. In other words as each starch granule swells its suffers profound attrition during the swelling, but owing to their dispersion in water the local heat generated by the shearing impacts is so reduced or dispersed that degenerative or depolymerizing influences characteristic, for ex- 6 in any conventional manner such as, for example, by spray or drum drying. The product resembles sugar in appearance and has the property. of

. going directly inte solution in cold water.

ample, of dry grindingare minimized. The fact that the progressively swellingI starch granules are rapidly and eliciently disorganized is `attested by the observation that the rate and the degree of viscosity increase, at this state, are very much less than with the normal cooking and agi- 'ature is preferable in order to obtain desired results. It will be apparent, also, that any external preheating may be omitted, if desired, but inasmuch as no material modification of the starch takes place prior to gelatinization, it is preferred to decrease the processing time by such a preheating step. f

It is preferred that the rate of heating should not be too rapid, so that the granules will notI to gelatinize or swell at a faster rate than they can be modiiied by the physical treatment and the degree or eiciency of the disorganization will be impaired. By permitting the milk of starch to be heated by the action of the pumping means alone, the disorganization process is believed to proceed at maximum eiiiciency.l

For convenience, the term processing index (I) is used herein to describe the rapidity with which it is preferred to circulate the starch during gelatinization. If for example the rated pump delivery be P gals/min., and the volume of the batch be B gals., the batch will be 'circulated P/B times/min. Since the' moist efficient processing appears to exist in the gelatinization zone, this time of most effective processing (T) multiplied by P/B (the pump/batch ratio) will give approximately the total number of complete circulations of the entire batch, i. e., what may be termed the processing index (I). The formula may be expressed:

P I TX B where B=batch volume in gals. a'nd P==rated pump capacity in gals. per minute.

For most starches, processing indexes greatly in excess of while promoting dispersio'ns of lower viscosity, appear to yield products less de'- sirable in nlm-forming properties. In most cases it is not desirable to exceed a processing index of 50. Certain types of starch, however, such as wheat starch, characterized by a gelatinization range extending over a relatively wide temperature range, must perforce suffer a considerably higher processing index than starches having the normally narrow gelatinization range. For tapioca, potato, or corn starches, an index of ously to starch of any source.

A more specific example of the method of the v invention may be considered in connection with the diagrammatic showing in Fig. l. In accordance with this example, 50 gallons of a starch milk is Amade by adding 54 pounds of potato starch` to 376 pounds 'of water. The mix is agitated and heated by live steam to 130 F. over a period of 13 minutes, as shown at a. The orifice was adjusted to give an initial pressure ,of 300 pounds per square inch, as shown at a'. The steam is then lshut-off and pumping started at 40 gals. per minute, the milk" of starch being continucirculated. Processing is now as shown at c, no attention being required save to note the lapse of time required for the opytimum processing index-in this example 25 minutes from the time the pressure starts to rise above the initial pressure, as shown at b. The

pressure increased to about 630 lbs. per square inch, as 'shown at e, in about 18 minutes from the time the pressure started to rise (b) and fell to about 609 lbs. per square inch at the end of the processing period, as shown at f. The temperature rose to about 168 F. at the end of the treatment, as shown at g. At the close of this last period (b-c) of 25 minutes (60 minutes in all), pumping is stopped and the kettle discharged. The processing index was The fluid, homogeneous starch dispersion is now ready for commercial application of-V sizing or coating, or may be stored for subsequent use.

A similar process can be carried outy with potato, tapioca or corn starch in a concentration preferably of about 10 to 15% solids with the same apparatus at about the same processing index. The maximum degree of desirable characteristics is obtained in concentrations of this order. l

The process of this invention may be applied When applied to 'different starches the factors will vary depending on the starch. For example, wheat starch, which has a higher gelatinizing temperature may be preheated to a higher degree and may require a high processing index, preferably at least 40.

The unusual stability of concentrated dispersions of the new starch product prepared in accordance with this invention is believed to be unique, both in respect to a wide range of temperature variations and to aging. 4

In order to show the novel viscosity characteristics of the starch prepared in accordance with the invention and to demonstrate the manner in which it, distinguishes from the starches known to the prior art, it is convenient to consider the viscosity characteristics of a dispersion of the `starch at different temperatures.

Y any solution is plotted against the reciprocal of approximately 15 to 25, determined as outlined above, seems preferable.

After the milk of starch has become completely gelatinized and disorganized by subjecting it to the process described, it may be dried the absolute temperature, a line or curve will be pbtained which is indicative of the viscosity properties of the liquid over the temperature range under consideration. In a 'so-called ideal fluid the relationship of the logarithm of the kinematic viscosity to the reciprocal of absolute temperature will be linear. Pure water approaches this linear relationship.

entirelyI automatic over a subsequent period of 47 minutes.

Ii a solution of a taploca or cassava starch prepared in accordance with the invention, having a concentration of 10% of solids, has its kinematic viscosity in `centistokes determinedby means of a suitable viscosimeter betweenwthe ranges of 10 C. and 80 C., and the logarithms of these viscosity values plotted against the reciprocal of the absolute temperatures, the relationship willapproach the linear, as shown at I in Fig. 2. This, indicates a remarkable degrec of homogeneity and stability of liquid structure.

If a aqueous dispersion of tapiocaor cassava starch processed or disorganized by normal methods of cooking, has its kinematic viscosity determined and similarly plotted with respect to absolutev temperature, the relationship does n ot remotely approach the linearas shown at `2 m Fig.

2., The percentage rate of change of viscosity Y is great at both extremes of the` temperature range, giving a curve of a sinusoidal form. This is more or less a. characteristic of the viscous behavior of the disorganized starches known in the prior art. The curve 2 indicates considerable heterogeneity of liquid structure and pronounced association effects probably through hydrogen bonding. It may also be noted that while the viscosities of the composition shown at I and 2 are similar at 80 C., the composition shown at l has'twice as much' solid content as the composition shown at 2. i

The novel characteristics of the starch product will also be apparent when it is compared with a so-called homogenized" starch paste prepared by known Vprocesses of long continued agitation or treatment in colloid mills of e. substantiallygelatinized starch paste. If, for example, a 10% Vconcentration of an aqueous dispersion of tapioca gives dispersions which have the smoothness and fluidity of a soluble dextrine, but nevertheless the exceptional strength and toughness of a, protective coating. I

Starch prepared in accordance with the lnvention forms a film which is more cellulosic-like v in character than a conventional starch im. Such film-forming properties in starch dispersions f are unique and valuable as shown by commercial tests made on paper and textiles.

The product of this invention should be Particularly applicable to sizing and coating operations, such as for textile and paper use, owing as heretofore stated, to a unique degree of homogeneit-y, viscous stability, and the fact that the starch is disorganized or dispersed rather than degenerated.

. It will also be understood that the product, whether in theliquid form or dried by suitable methods, may be more. or less further converted' by`i'amiliar processes, such as by amylases, heat and/or chemicals, etc., such conversions havingA the purpose of modifying it for special industrial usages. Thus, the viscosity for certain purposes .suchas paper coating, might be reduced by en- I forming a slurry of raw starch having a concenor cassava our is processed by pumping prege i latinized paste through a nozzle for a very long period of time, andthe kinematic viscosity dei termined at temperatures of 10 to 80 C., not only is the. viscosity much less than the product of the invention, but when the logarithms of the kinematic viscosity are plotted against reciprocals of absolute temperature, the ,location and form of the curve may be entirely different, as shown at 3. This form of relationship of viscosity to temperature is in part typical of the so-called thinboiling starches. f

Still another variety of degraded starches are those which tend to yform a paste or gel upon cooling. In these starches the percentage change of viscosity rises very rapidly at lower.tempera. tures and the logarithm of kinematic viscosity plotted against the reciprocal of yabsolute temperature deviates pronouncedly from a straight line relationship in the lower temperature ranges.

Thus the viscosity-temperature relationship for the product of the invention is unique and entirely different from the vlsco'sityftemperature relationship of dispersions of starch preparedin accordance with priorart processes within the temperature range of 10 C. and 80 C.

The viscosity stability of the product o! the invention is also unique. A 10% concentration of a root starch prepared in accordance withthe 4 invention, such as tapiocaor potato starch, shows a very reduced tendency to thicken 'or retrograde upon long standing. This is a very desirable commercial attribute.

The homogeneity of the starch prepared in accordance with the invention as indicated by the viscosity-temperature relationship is reiiected by rexceptional film-forming properties. Such starch tration of about 5 to 30% solids, ,repeatedly pumping the slurry under pressure through a restricted orifice to heat the slurry to a gelatinizing temperature as the starch is subjected to attrition in passing through the oriilce.

2. Amethodof treating starch comprising formfing a slurry of raw starch having a concentration of about 5 to 30% solids and pumping the slurry through a restricted orifice, said pumping being carried out to create an initial pressure of at least 300 lbs. per square inch and continuing the pumping .to achieve a processing index of not more than 50, said processing index being the time in minutes during which the slurry is pumped after an increase in pressure begins multiplied by the capacity of the pump in gallons per minute and divided by the total volume of the slurry in gallons.

3. A method of forming a novel starch product which comprises preparing a slurry of starch inV suflicient water to gelatinize substantially all o! the starch, and continuously pumping said slurry under pressure through a restricted orice during y gradual gelatinization of the starch, at least part of said gelatlnization being caused by pumping of the slurry under pressure through said restricted orifice.

4. A method of forming la novel starch product comprising forming a starch slurry having a concentration of .about 5 to 30% solids, and repeatedly forcing the slurry under pressure through a restricted oriiice While the slurry is gradually raised in temperature through the gelatinization zone, at least a part of the increase in temperature .being caused by forcing the yslurry under pressure through said n restricted oriiice.v

5. A method of treating raw starch comprising animee pumping a slurry of the starchhaving 5% to 30% solids through a restricted orifice at an initial 1o l .9. A method of treating starch comprising initially heating a slurry of raw starch having 5% temperature below the gelatinization temperatemperature below the gelatinization temperature to 30% solids to below the gelatinization temperature of the starch and thereafter continuing said heating solely by recirculating the starch slurry under an' initial pressure of about 300 lbs. per

' square inch through a restricted orice until subof the starch and at an initial pressure of not less than 300 lbs. per square inch, and continuing the pumping until there is no increase in pressure when pumping at constant volume.

7. A method o f treating starch which comprises preparing a slurry of a raw starch in sucient water t gelatinze substantially al1 of the starch, raising the temperature of said slurry'through gelatinization solely by recirculating said slurry under pressure through a restricted oriilce until there is no further increase in viscosity of the resulting dispersion.

8. A vmethod of treating starch comprising initially heating a slurry of raw starch having to 30% solids to below the gelatinization tempera'- ture of the starch and thereafter continuing said heatingsolely by recirculating the starch slurry under pressure through a restricted orice until substantially all of the starch is gelatinized.

stantially all of the starch is gelatinized.

GEORGE V. CAESAR. THOMAS D. THOMPSON.

REFERENCES CITED The following Areferences are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date Re. 21,057 Caesar Apr. 25, 1939 1,947,295 Jasga Feb.. 13, 1934 2,105,052, Oltmans J an. 11,1938 1,418,275 Benjamin June 6, 1932 2,214,018 Gill Sept. 10, 1940- 2,224,355 Moller Dec. 10, 1940 2,216,179 Bauer Oct. 1, 1940 1,851,749 Bergquist Mar. 29, 1932 2,121,502 Kassler June 21, 1938 2,137,169 vLevey Nov. 15, 1938 2,313,574 Payne Mar. 9, 1943 

